2,4-Difluoro-1-iodobenzene → HCID 86728285, compound

HRID 1776902Notes

Reaction equation

HRID 1776902 reaction equation
[F:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1I.[NH2:10][C:11]1[C:37]([Br:38])=[CH:36][C:14]2[C:15]([C:31]([O:33][CH2:34][CH3:35])=[O:32])=[C:16]([Sn](CCCC)(CCCC)CCCC)[O:17][C:13]=2[CH:12]=1>C1(C)C=CC=CC=1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[NH2:10][C:11]1[C:37]([Br:38])=[CH:36][C:14]2[C:15]([C:31]([O:33][CH2:34][CH3:35])=[O:32])=[C:16]([C:3]3[CH:4]=[CH:5][C:6]([F:8])=[CH:7][C:2]=3[F:1])[O:17][C:13]=2[CH:12]=1

Participants

5

Reactant 2

HCID 1375192,4-Difluoro-1-iodobenzeneHCID 86728286HCID 86728286, compound

Product 1

HCID 86728285HCID 86728285, compoundYield 9%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

2,4-difluoro-1-iodobenzene (2.09 g, 8.72 mmol) and Pd(PPh3)4(20 mg) were added into a solution of ethyl 6-amino-5-bromo-2-(tributylstannyl)benzofuran-3-carboxylate (5 g, 8.72 mmol, prepared from ethyl 6-amino-5-bromobenzofuran-3-carboxylate with LDA and Bu3SnCl) in toluene (10 mL) under N2, then the mixture was stirred at 60° C. overnight. The reaction mixture was cooled to room temperature and filtered. The filtrate was washed with H2O, brine, dried over Na2SO4. After concentrated, the resulting residue was purified using column chromatography (petroleum ether:EtOAc=6:1) to provide the product of ethyl 6-amino-5-bromo-2-(2,4-difluorophenyl)benzofuran-3-carboxylate (310 mg, yield: 9%). 1H-NMR (CDCl3, 400 MHz) δ 8.10 (s, 1H), 7.66 (d, J=8.0 Hz, 1H), 6.95˜7.01 (m, 2H), 6.92 (d, J=8.0 Hz, 1H), 4.37 (q, J=7.6 Hz, 2H), 1.33 (t, J=7.6 Hz, 3H). MS (M+H)+: 396/398.

Workup

  1. temperatureThe reaction mixture was cooled to room temperature
  2. filtrationfiltered
  3. washThe filtrate was washed with H2O, brine
  4. dry with materialdried over Na2SO4
  5. concentrationAfter concentrated
  6. customthe resulting residue was purified

Sources & evidence

ORD record
ord-9bff500f18304747b86ba1eb26ad2dcf
Source dataset
uspto-grants-2016_02
Patent number
US09265773B2

Reaction notes

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